Applied Catalysis A: General 280 (2005) 125–131

Complete benzene oxidation over Pt-Pd bimetal catalyst supported on

␥-alumina: influence of Pt-Pd ratio on the catalytic activity
Hyoung Sik Kim a,∗ , Tae Won Kim b , Hyoung Lim Koh c , Seo Ho Lee a , Byoung Ryul Min a
a Department of Chemical Engineering, Yonsei University, 134 Shinchon-Dong, Seodaemoon-Gu, Seoul 120-749, Republic of Korea
b Department of Chemical Engineering, RICT, Hanseo University, Seosan, Republic of Korea
c Hyosung Chemical Technology RandD center, Anyang 431- 080, Republic of Korea

Received 3 September 2003; received in revised form 17 February 2004; accepted 24 February 2004
Available online 4 January 2005

Abstract

Pt-Pd bimetal catalysts were prepared in order to develop and investigate catalysts with excellent activity and stability for benzene destruction.
In the reaction results, the addition of Pt to Pd/␥-Al2 O3 catalyst brought about the increase of catalytic activity. Moreover, it was effective in
preventing the deactivation of the catalysts in benzene combustion. The addition of some amount of Pt made Pd particles available for better
benzene combustion. On the contrary, the addition of Pt beyond a certain amount decreases activity because of the Pd active sites overlapped
with the Pt active sites. The activity of the catalysts is related to oxidation state of metal, Pd/Al ratio and particle size on ␥-Al2 O3 . These
effects of Pt addition to Pd catalysts were studied by XPS, XRD, and TEM analyses.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Combustion; Platinum; Palladium; XPS

1. Introduction Table 1 shows VOC abatement techniques. VOC abate-

Volatile organic compounds (VOCs) are known as one of
the major contributors to air pollution. The Clean Air Act
(CAA) amendment of 1990 is intended to reduce emissions
of volatile organic compounds by 70–90%. It specifically
names 189 compounds as hazardous air pollutants (HAPs)
[1,2].
Control of volatile organic compound emission is impor-
tant because they are a principal component in the chemical
physical atmospheric reactions that form ozone and other
photochemical oxidants [3,4]. Benzene, one of the repre-
senting VOC materials, is broadly used as a constituent in
motor fuels, and as solvent for fats, paints, and plastics and
is also used in the manufacture of detergents and explosives.
Since benzene causes diverse diseases and both structural
and numerical chromosomal aberrations in humans, so ben-
zene emitted from various sources must be removed effec-
tively [5].
∗ Corresponding author. Tel.: +82-22123355427; fax: +82-23126401.
E-mail address: dino1@yonsei.ac.kr (H.S. Kim).
ment technique can be classified into thermal oxidation, ad-
sorption, absorption, condensation, bio-filtration, catalytic
oxidation and other new techniques [6,7].
Thermal oxidation is the simplest method but it must
be carried out at high temperature, typically over 1000 ◦ C.
Therefore, this method requires high capital cost and high
operating cost. Adsorption is a very useful method in re-
covering expensive solvents and operating in large capac-
ity. But it also requires high capital cost and operating cost.
Catalytic oxidation can be operated at lower temperatures,
typically 300–600 ◦ C. Also, catalytic oxidation is the most
useful method to destruct VOCs because it requires rela-
tively inexpensive cost and is easy to be applied to various
processes.
In catalytic oxidation, the most important factor is the
selection of the catalysts. Supported noble metal catalysts
have been known as highly active catalysts for oxidation
reactions and have been preferentially used in commercial
practices in spite of their cost [8,9]. Particularly, platinum
or palladium on ␥-Al2 O3 has been widely used for the oxi-
dation of VOCs, other than c-VOC. Platinum has been effi-
ciently applied to the abatement of hydrocarbons, especially
of aromatic hydrocarbons [10,11]. Also, palladium catalysts

0926-860X/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.02.027
126 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125–131

Table 1 Table 2
Characteristics of various techniques for VOC abatement Notation of sample
Technique Characteristic Notation Prepared condition
Capital cost Operating cost Flexibility 05Pd-r 0.5 wt.% Pd on (␥-Al2 O3 ) reduction
of process 2Pd-a 2 wt.% Pd on (␥-Al2 O3 ) after reaction
Incineration High High Good 03Pt-r 0.3 wt.% Pt on (␥-Al2 O3 ) reduction
Adsorption High Medium Good 1Pt-a 1 wt.% Pt on (␥-Al2 O3 ) after reaction
Absorption Low Medium Bad 03Pt2Pd-r 0.3 wt.% Pt 2 wt.% Pd on (␥-Al2 O3 ) reduction
Condensation High Medium Bad 1Pt05Pd-a 1 wt.% Pt 0.5 wt.% Pd on (␥-Al2 O3 ) after reaction
Bio-filtration Medium Low Good 3Pt2Pd-r 3 wt.% Pt 2 wt.% Pd on (␥-Al2 O3 ) reduction
Catalytic oxidation Medium Medium Good r: sample reduced in a H2 before reaction; a: sample after reaction.

have been extensively recognized to be the most active metal
for methane oxidation, VOCs combustion and CO oxidation
[12].
In commercial applications, catalytic stability as well as
activity, is a very important factor. However, the duration of
the catalysts is not enough in noble metal catalysts, because
supported Pd and Pt particles become easily sintered and
poisoned at relatively low temperature [13]. The sintering of
metal particles results in a loss of the metal on surface area,
hence the catalyst deactivation increases.
The present work extended the development of noble
bimetal catalysts that have an excellent activity and stability
higher than that of Pd or Pt mono-metal catalysts in benzene
combustion. The object of this paper is to study the influ-
ence, activity and stability of the Pd catalysts with the addi-
tion of Pt. We have used X-ray photoelectron spectroscopy,
X-ray diffractometry and Transmission Electron Microscopy
as tools of analyzing the surface composition and the chem-
ical states of metal components to investigate the relation-
ship between the cause of changes of stability and activity
and different Pt-Pd catalysts.
2. Experimental
All metal catalysts were supported on ␥-Al2 O3 (BET
area, 241 m2 /g s) which had been dried in an oven for 24 h
at 120 ◦ C. All catalysts were prepared by excess wetness
impregnation using an aqueous solution of hexachloropla-
tinic acid (H2 PtCl6 ·nH2 O, Aldrich) and palladium chloride
(PdCl2 , Aldrich). The impregnated catalysts were dried in
an oven for 24 h at 120 ◦ C and then calcined for 4 h at 500 ◦ C
in air. The calcined catalysts were subsequently reduced in
a H2 flow with rate of 50 ml/min at room temperature and
at 400 ◦ C for 2 h (Table 2).
The catalysts referred to by the designation mPtnPd,
where m and n indicate the weight percent, were prepared
by the procedure described above.
2.1. Catalytic test
The oxidation of benzene over the catalyst was carried out
in an isothermal fixed-bed continuous-flow reactor to test
catalytic reactivity of the catalysts. The reactor system con-
sists of a vertical tubular furnace, 30 in length controlled by
a PID controller. The reactor itself is a quartz tube of 6 mm
i.d. The catalyst bed is located in the middle of the reactor.
A thin thermocouple was used for an accurate measurement
of reaction temperature. All gas lines of the reaction system
are heated to 75 ◦ C in order to avoid VOC adsorption and
condensation on tube walls.
The reactant was benzene/air mixture gas (1000 ppm ben-
zene in air, 1 bar). The procedure for each experiment was
as follows: the catalyst sieved in the 100–200 mesh range
(in order to avoid mass or heat transfer effects) was placed
in the reactor supported by quartz wool and the reactor was
heated to 500 ◦ C at 10 min−1 under air flow and the tem-
perature was maintained for 2 h to calcine the catalysts.
Then the catalyst was cooled to room temperature under
He flows. The flow was then switched to H2 and the tem-
perature was raised to 500 ◦ C and maintained for 60 min.
Subsequently, the catalyst was cooled under the H2 flow to
room temperature; then the catalytic test were performed in
the 150–350 ◦ C temperature range under atmospheric pres-
sure using 1000 ppm C6 H6 in air(O2 : 20%, N2 : 80%). VOC
destruction efficiency as a function of reaction temperature
was measured at 15 000 h−1 . All gases were controlled by
mass flow meters. Reactants and reaction products were an-
alyzed by gas chromatograph (HP5890A, Hewlett-Packard)
with a FID detector.
2.2. Characterization of the prepared catalysts
X-ray diffraction experiments were performed on a stan-
dard Rigaku diffractometer using CuK radiation. The cal-
cined samples were scanned in the 2θ range of 10–80◦ . A
proportional counter and a 0.04◦ step size in 2θ were used.
X-ray photoelectron spectroscopic measurement was car-
ried out in an ESCALAB 2201-XL (Fision) equipped with
the aluminum anode as unmonochromatized X-ray source
(1486.6 eV run at 10 kV and 15 mA, fixed analyzer trans-
mission). Before the XPS analysis was begun, some samples
were treated at 500 ◦ C for 1 h under H2 to be reduced and
then cooled in H2 to room temperature. After the reaction
other samples were cooled to room temperature under He
flow. All samples were made airtight.
TEM images of catalysts before and after reaction were
acquired with a JEOL TEM-200CX transmission electron
microscope. Suitable transmission specimens were prepared
 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125–131 127

by dispersing the catalyst powders in non-polar solvent
(ethanol) and placing a drop of the suspension onto a carbon
film supported on a 200 mesh copper grid.
3. Results and discussion
All catalysts were pretreated with hydrogen. Earlier re-
sults indicated that hydrogen treatment may cause Pd en-
richment on surfaces [14].
Fig. 1 shows comparison of light-off curves over different
Pt-Pd catalysts. Pt-Pd bimetal catalysts have better conver-
sion values than mono-metal catalysts. Pt-Pd bimetallic cat-
alysts have a good conversion due to the synergetic effect of
Pd metal and Pt metal. 03Pt2Pd catalysts have the most ex-
cellent activity among Pt-Pt bimetal catalysts. As shown in
Fig. 2a–c, there is a close relation between Pt/Pd ratio and
the shape of the conversion. mPt-nPd catalyst with relatively
large Pt/Pd ratio gradually becomes similar to the shape of
the conversion on mPt mono-metal catalysts. For example,
the shape of the 3Pt0.5Pd curve in Fig 2c is more similar to
the shape of the 3Pt curve than to that of 3Pt2Pd.
Pd particles on Al2 O3 surfaces were covered with Pt in
bimetal catalysts containing excess Pt loading. The activity

Fig. 1. Light-off curves for benzene combustion over mPt2Pd and 03PtnPd. (m: 0.3, 1, 0 n: 0.5, 1, 2).

Fig. 2. Light-off curves for benzene combustion over (a) 03PtnPd (b) 1PtnPd (c) 3PtnPd (n: 0, 0.5, 2).
128 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125–131

Table 3
Conversion of benzene of pretreated catalysts and catalysts after reaction
at 250 ◦ C
First run: H2 Second run: recycle
pretreatment (10% H2 , test after reaction (%)
90% N2, 500 ◦ C, 2 h) (%)
03Pt-r 87.23 86.89
2Pd-r 76.68 74.8
03Pt-2Pd-r 99.5 99.0

of bimetal catalysts with excess Pt loading decreases, though

commonly, the activity of Pt is superior to that of Pd in VOCs
oxidation. This result is consistent with the XPS results.
Table 3 shows the activity of the pretreated samples and
the samples recycled after the reaction. The activities of
03Pt catalysts and 03Pt2Pd catalyst had little change in the
second run compared to the first run. But the activity of 2Pd
catalysts in the second run is lower than that in the first run.
This result is said to be related to the oxidation state of Pt
and Pd [15,16].
Fig. 3 shows the time-course of the catalytic activities of
supported 2Pd and 03Pt2Pd catalyst in benzene combustion
at 350 ◦ C for 48 h. The 2Pd/␥-Al2 O3 catalyst had high ac-
tivity similar to that of 03Pt2Pd catalysts in the beginning, Fig. 3. Stability test of 2Pd and 03Pt2Pd catalysts for 48 h.
but the activity decreased gradually with time on stream. On
the other hand, the 03Pt2Pd/␥-Al2 O3 catalyst kept up the shown in Fig. 4. The prepared catalysts before reaction and
same high activity for 48 h. We confirmed that the addition catalysts after reaction show an amorphous peak. This re-
of Pt on Pd/␥-Al2 O3 catalyst can bring about the increase sult indicates that metal particles on ␥-Al2 O3 are highly dis-
of catalytic activity as well as the prevention of the catalyst persed. Broad and diffuse diffraction lines of catalysts in-
from deactivation in benzene combustion. dicate amorphous crystal peaks of ␥-alumina. In agreement
The crystallinity of Pd and Pt was investigated by XRD. with the formerly reported results, we have authenticated
The effect of the Pd:Pt atomic ratio on phase formation is that low Pd, Pt loading on high surface area supports, such

Fig. 4. XRD profiles of catalysts.

 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125–131
Fig. 5. TEM image of (a) 03Pt/␥-Al2 O3 (b) 2Pd/␥-Al2 O3 and (c) 03Pt2Pd/␥-Al2 O3 .
as ␥-Al2 O3, are highly dispersed [17]. Therefore, Pt and Pd
peaks were not detected by XRD.
In TEM analysis, we observed the changes of particle
size and morphology in Pd catalyst with Pt loading. It was
reported that the particle growth of supported Pd particles
proceeded through the migration and coalescence of crystal-
lites [18]. But in this study, no distinct change was observed
before and after reactions, due to the low operating temper-
ature. As shown in Fig. 5a–c, 2Pd and 03Pt have irregular
crystalline structures and particle sizes but 2Pd catalysts with
03Pt have a uniform structure and particle size. The forma-
tion of small particles and uniform size distribution are sup-
posed to increase the activity. These effects were attributed
to the higher dispersion of supported particles and the sup-
pression of the particle growth. This result is in agreement
with XPS results, Table 3 and Fig. 4 (deactivation test).
All XPS peaks have been fitted by the Gaussian–Lorentzian
method, after background subtraction using the Shirley
method. The XPS peaks were analyzed in terms of relative
peak area intensity and chemical shifts of Pd and Pt. Quan-
titative analyses of the peaks were carried out by adopting
suitable atomic sensitivity factors [19,20]. The asymmetry
of the Pd 3d peak in the fitting curve was considered by
using the Gaussian–Lorentzian function [21].
The C 1s binding energies for various catalysts did
not change significantly. The C 1s spectra of samples
have the same shapes and nearly the same full-width at
half-maximum (FWHM) value range. The charging effects
were corrected by C 1s peak as a reference for all samples
at binding energy of 284.8 eV. The Pt catalyst charging was
eliminated by referencing all the binding energies to the
Al 2p core level energy from the support, because the Pt
Table 4
The Pd 3d, Al 2p and O 1s binding energies (eV), the surface concentration and the chemical state of palladium
2Pda 2Pd-r 2Pd-a
Pd 3d5/2 335.1 335.7 336.55
(Pd/Al)XPS – 0.0443 0.0419
Pdm /(Pdm +Pdo ) – 0.6117 0.4912
Determined by deconvolution of XPS Peak 4.0 program.
a Referrence data [21].
129
peak and the Al peak overlap each other by around 75 eV.
But the Pt peak cannot be deconvoluted due to the snall Pt
content. So this study was focused on the analysis of Pd 2p
peak in catalysts.
In Table 4, the Pd 3d binding energies of the catalysts
and curve fitting results are listed. Table 4 shows Pd 3d
binding energy, shift, Pd metal ratio, and Pd/Al of catalysts
containing different amounts of platinum before reaction and
after reaction. The deconvoluted peaks are calculated by the
program of XPS Peak 4.0.
Among the catalysts reduced, the binding energy of
03Pt2Pd-r (335.5 eV) was slightly lower than that of
1Pt2Pd-r (336.0 eV), 3Pt2Pd-r (335.85 eV) and 2Pd-r
(335.7 eV). Also the Pd metal ratio (Pdm/Pdm + PdOx ) of
03Pt2Pd-r catalysts shows the highest compared to 1Pt2Pd
and 2Pd. These results show that Pd state of 03Pt2Pd-r cata-
lysts was shifted more toward metallic state (Pd◦ ) than other
catalysts after reduction. The binding energy of Pd 3d on all
catalysts is shifted to a higher level after reaction. Pd state
of all catalysts after reactions was shifted more toward PdO.
The binding energy values of all catalysts after reactions
are similar to each other, ranging around 336.55 ± 0.15 eV.
There is no difference among the oxidation states of all
catalysts after reactions.
Fig. 6 shows the relative intensities of the spectra of Pd
3d catalysts with different Pt, Pd loading weights before re-
action. The relative intensity of Pd 3d spectra in catalysts
with increasing Pt contents gradually decreased (2Pd >
03Pt2Pd > 1Pt2Pd > 3Pt2Pd). There is a close correlation
between these results and the activity values of catalysts.
Figs. 7 and 8 display XPS peak deconvolution results
before and after reaction of 03Pt2Pd and 2Pd. As shown in
03Pt2Pd-r 03Pt2Pd-a 1Pt2Pd-r 1Pt2Pd-a 3Pt2Pd-r
335.5 336.60 336.0 336.8 335.85
0.0413 0.0414 0.0397 0.0317 0.0258
0.6393 0.5355 0.5549 0.4732 0.5225
130 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125–131

Figs. 6 and 7 and Table 3, results of deconvolution show that

the Pd/Al ratio of Pd 3d peak in 03Pt2Pd had little change
after reactions compared to that of Pd 3d peak in 2Pd. Also
the metal ratio of 03P2Pd-r was kept after reactions unlike
the metal ratio of other catalysts. From these XPS results
and activity results, we suppose that the metal ratio of Pd
and Pd/Al ratio are closely related to activity.
Under excess oxygen, oxidation and reduction are con-
tinually repeated during the reaction. Benzene is oxidized,
and Pd catalyst supported on alumina can easily undergo a
phase transformation between the metallic Pd and the oxi-
dized PdO state during the reaction [22,23]. But the reason-
able addition of Pt maintains Pd metal state and Pd/Al ratio
under low temperature and excess oxygen. It is known that
Pd easily changes to oxidized PdOx commonly under the
excess oxygen and low temperature.
Therefore these results presume the addition of suitable
Fig. 6. Pd 3d spectra of mPt-nPd catalyst before and after reaction.
amount of Pt made Pd to take an optimum state for benzene
combustion. On the contrary, the addition of Pt beyond a
certain amount decreases the activity because of the Pd active
site overlapped with Pt.

Fig. 7. Curve fitting of Pd 3d spectra of 2Pd-r catalyst and 03Pt2Pd before and after reaction (a) 03Pt2Pd-r and (b) 03Pt2Pd-a.

Fig. 8. Curve fitting of Pd 3d spectra of 2Pd-r catalyst and 03Pt2Pd before and after reaction (a) 2Pd-r and (b) 2Pd-a.
 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125–131
4. Conclusion
In the XRD and TEM results, the high dispersion and
the formation of small particles and the uniform size dis-
tribution in bimetal catalysts are supposed to increase ac-
tivity and stability because the Pt addition has an influence
on the interaction between the Pd and the support. In XPS
results, Pd/Al ratio of 03tP2Pd-r having the best activity
did not shift after reaction and the metal ratio of 03Pt2Pd-r
was kept after reaction better than those of 1Pt2Pd-r or 2Pd
catalysts.
Pt-Pd bimetallic catalysts are superior to monometallic
Pd, Pt catalysts due to having both Pt active site and Pd
active site in catalytic activity. 03Pt2Pd bimetallic catalyst is
the most active and stable catalyst in benzene combustion.
The most important factor in keeping activity and stability
is the optimum ratio of Pt and Pd. The addition of a suitable
amount of Pt modified Pt-Pd bimetal catalysts to achieve
the optimum state for benzene combustion, but the addition
of Pt beyond a certain amount decreased the activity due
to blockage of active sites (overlapped Pt, Pd active sites).
Therefore an optimum loading weight exists for benzene
combustion.
Acknowledgements
Financial support from the Yonkang Foundation is grate-
fully acknowledged.
131
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